Perchlorocarbon having the empirical formula c10cl10



7 United States wide ranges without -Qntaii1i-ngabout-0:001 tdabout"0.5"percent by'weight a 2,908,723 Patented Oct. 13, 1959 PERCHLOROCARBQN HAVING THE ENIPIRICAL 3 Claiins. ((11.260-648) V This invention relates to a new chemical compound composed of carbon and chlorine, having an empirical formula of' C Cl n More particularly, this invention relates to a new chemical compound bis-(pentachlorocyclopentadienyl) having an empirical formula C Cl and a melting point of about 120 to 122 degrees centigrade.

The compound of this invention may be prepared by reductive-coupling of hexachlorocyclopentadiene by hydrogen in the presence of a noble metal of group VIII having an atomic weight greater than 43 as 'a catalyst, with or without a solvent, at a temperature above about 20 degrees centigrade."

In preparing the compound of this invention, presume ably inaccordance with the following equation:'

a solvent may or may not be employed; if a solvent is used, it should be inert with respect to the reactants and the reaction "roducts. .Amon the solventswhich H P g 7 black filtrate was cooled to 12 degrces 'centigrade, then maybe employed are inexpensive and unreactive materials "inert under the conditions employed, such as beniene; toluene, etc. o Q yl have found that "the "choice of the catalyst is re- 'trictedf to noble metals in group VIH of the periodic table whichhave an atomic'number greater than 43. These metals are ruthenium,irhodium, palladium, osmium, radium andplat inum whose atomic numbers are 44, 45, 45, 76,771 and 78 respectively. I have found palladium to be themost satisfactory of these catalysts as well as being one of the least expensive of'the'se'particular elements. The catalyst to be used in 'the method "of this invention is most effective When itis' deposited on an inert carrier, such .asactivated A alumina, activated charcoal or a finely divided st ate. metal depositedion the carrier may be varied within materially effecting the reaction.

ki'eselguhr preferably in I prefer to: use asa palladium. deposited therein in the amount of about 5 percentjby. Weight. After treatment of the product the catalyst-011 theinert carrier or deposited catalyst is removed byyhot filtration. Such deposited catalysts are available inficommerical forms ranging from} to 20 .percent ofa noble. metaldeposited on-the inert carrier. The concentrationof the catalyst to be used during the reductive coupling may be varied in wide ranges without reaction; in'generalfthe catalytic F th I.

ur ermore chlorine content of, 74.60 percent o e: amount of group VIII noble carrier of powdered charcoal-With serve to increase the yield of by-products The compound of this invention is useful as a chemical intermediate, for example, C Cl may be chlorinated to produce (3 C1 having a melting point of 221 to 223 degrees centigrade as more fully described hereinafter, which material is disclosed and claimed in copending application, SerialNo. 518,397, filed of even date herewith in the name of Earl T. McBee and James D. Idol, Jr. Further, C Cl may be thermally dechlorinated to produce C Cl Still further, C Cl is useful as an insecticide as exemplified hereinafter.

EXAMPLE 1.PREPARATION Twenty grams of hexachlorocyclopentadiene and one gram of catalyst consisting of 5 percent palladium-oncarbon powder, were charged into a two liter round bottom flask equipped with a thermometer, a reflux condenser, and a heating or cooling means. Gaseous hydrogen was bubbled into the mixture with stirring at a temperature of 30 to 40 degrees centigrade. The eflluent gases were scrubbed with water to remove any hydrogen chloride evolved. After six hours, one mole of hydrogen chloride was evolved for every four moles of hexachlorocyclopentadiene charged and'the reaction was stopped. The catalyst was removed by filtration at a temperature or 28 degrees centigrade. The resultant 5.8 grams of the white crystalline product (30% by The. product was recrystallized from isopropyl alcohol and then from hex.-

' ane to give 5,6 grams of odorless crystals (28%). These of the metal based on the weight of the starting material 4 catalyst may be re 7 crystals were analyzedjand found to possess a melting point of about to 122 degrees Centigrade, a chlorine content of 74.2 percent by weight, a molecularweight of '4'6 0; which corresponds to C Cl having a theoretical theoretical molecular weight of 475, respectively.

The method of Example .1 was repeated except that 20 grams of hexachlorocyclopentadiene was dissolved in toluene in the presence of a palladium-on-carbon catalyst. The product was recovered as in Example 1 and containedf5.9 grams of odorless crystals. These crystals were admixed, with the product of Example 1 and showed no depression of melting point.

' EXAMPLE 3.' 'UsE-As CHEMICAL INTERMEDIATE .or-c gi as colorless; needl'es', melting point of '22l t6 7 223 degrees centigrade.

6 C1 is disclosed in copendlng application, Serial No. 518,397, filed of even date herewith in the name of Earl T. McBee and James D. Idol, Jr. a

by weight, and a.

After cooling thetube Was to 346 degrees centigrade.

'2 EXAMPLE 4.USE AS CHEMICAL INTERMEDIATE A solution of 50 grams of 0 01 prepared as in Example 1 in 200 milliliters of carbon tetrachloride was placed in a Vycor tube 50 millimeters in-diameter by 250 millimeters long, equipped with a gas dispersion disk, internal cooling coils and a reflux condenser. The tube was irradiated by two fluorescent lamps while chlorine was admitted into the solution for twelve hours while maintaining the temperature at approximately degrees centigrade, after which the solution was recovered from the tube and the solvent evaporated. The residue was dissolved in 150 milliliters of benzene, decolorized with Norite, then filtered. The clear filterate was heated to remove benzene which resulted in the formation of colorless needle-like crystals. These colorless crystals were analyzed and found to possess a melting point of about 221 to 223 degrees centigrade, a chlorine content of 78.05 and 77.89 percent by weight; a carbon content of 22.12 percent by weight, which corresponds to C Cl having a theoretical chlorine content of 77.98 percent by weight and a theoretical carbon content of 22.01 percent by weight. Four grams of C Cl (0.007 mole) prepared as above was dissolved in 100 milliliters of methylene chloride, distilled from anhydrous aluminum chloride. Powdered aluminum chloride (0.5 gram) 'was added and the mixture was refluxed overnight. 'A darkened mixture was poured into water which had been made acidic with hydrochloric acid, then the organic layer was separated and washed with water and dried. Evaporation of the solvent left 3.7 grams of very light yellow crystals with a melting point of 485 degrees centigrade. An equal mixture of this product and that prepared as in Example 1, of a copending application filed ofeven date herewith in the name of Arnold N. Johnson did not result in a depressed melting point.

EXAMPLE 5.- USE AS CHEMICAL INTERMEDIATE ture of 250 to 270 degrees centigrade for ten hours in an electric furnace, after which it was removed from the furnace, cooled in a dry ice bath, openedand the contents extracted with 100 milliliters of chloroform. The resulting slurry was filtered and the filtrate evaporated to dryness leaving 1.5 grams of a crystalline residue. The crystals were recrystallized from carbon disulfide and found to possess a melting point of 344 The original precipitate was recrystallized twice from a 50:50 mixture by volume of benzene and glacial acetic acid. Thirteen grams of solid in insecticidal compositions, contributing high knockdown quality thereto. The dust is equally effective against other species of insects and this example is not to be construed as limiting the insecticidal usefulness of the compound.

The compound of this invention is capable of being diluted with a solvent, such as benzene, to form solutions or dispersions which are effective against mites, such as T etranychus atlanticus, and T etranychus bimaculatus. This new insecticide may be applied in any of the conventional methods. Thus, for example, it may be used in an aqueous emulsion or it may also be incorporated in organic liquids such as the aromatic hydrocarbons for spraying purposes. It may be effectively used in dusts with such inert solid diluents as kieselguhr, wood flour, walnut shell, talc and the like. More particularly, 0.2 gram of C Cl as in Example 1, may be mixed with a solvent, such as benzene, and an emulsifying agent to form an emulsifiable formulation which is then diluted to 200 milliliters with water. The following table shows the kills obtained under comparable conditions for the various dilutions when the sprays were applied to specific mites.

It is to be understood that the invention is not limited to the specific examples which have been offered merely as illustration and that modification'may be made within the scope of the appended claims without departing from the spirit of the invention.

I claim: v

1. The process for preparing a perchlorocarbon having the empirical formula C Cl and a melting point of 120 to 122 degrees centigrade which comprises the reductive coupling at a temperature of about 2 0 to about 40 degrees centigrade of hexachlorocyclopentadiene by treatment with hydrogen in the presence of a noble metal of group VIII having an atomic weight greater than 43, said metal being in the metallic state and supported on a carrier selected from the group consisting of actiwhite crystalline material were recovered representing an overall yield of 85 percent by weight. These white crystals were analyzed and found to possess a melting point of 345 to 347 degrees centigrade, a chlorine content of 70.12 and 70.15 percent by weight which corresponds to 0 01 having a theoretical chlorine content of 70.3 percent by weight. C Cl is disclosed in copending application, Serial No. 518,350, filed of even date herewith in the name of Charles F. Baranauckas.

A 25 percent by weight dust of the perchlorocarbon, C CI prepared as above, having a melting point of 345 to 347 degrees centigrade was made by intimately mixing the perchlorocarbon with a solid inert carrier, such as talc. This formulation which had the C Cl as the only insecticidal active ingredient produced a 100 percent knock-down in a period of twenty-four hours,

when applied in a contact knock-down test to the confused flour beetle (Tribolium confusium). This indicates the usefulness of the compound as an ingredient vated alumina, activated charcoal and kieselguhr, n0 solvent other than a hydrocarbon solvent being employed.

2. The process according to claim 1 wherein the-noble metal catalyst is palladium on activated charcoal. I

3. The process according to claim 1 carried out in the presence of toluene. 1

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Borsche et al.: Ber. der deut. Chem. jGesell., vol. 48,

pp. 452-8 1915). McBee et al.: Iour. Amer. Chem. Soc, vol; 77,- pp. 38991 (1955).

i UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2 908,???) October 13, 1959 J0hn.T., Rucker .It is hereby certified that error appears in theprinted specification of the above "numbered patent requiring correction and that the said- Letters Patent should read as corrected below.

milliliters; read millimeters Column 3, line 42-, for

Signed and sealed this llth day of April 1961,

(SEAL) Attest;

ARTHUR W. CROCKER 

1. THE PROCESS FOR PREPARING A PERCHLOROCARBON HAVING THE EMPIRICAL FORMULA C10CL10 AND A MELTING POINT OF 120 TO 122 DEGREES CENTIGRADE WHICH COMPRISES THE REDUCTIVE COUPLING AT A TEMPERATURE OF ABOUT 20 TO ABOUT 40 DEGREES CENTIGRADE OF HEXACHLOROCYCLOPENTADIENE BY TREATMENT WITH HYDROGEN IN THE PRESENCE OF A NOBLE METAL OF GROUP VIII HAVING AN ATOMIC WEIGHT GREATER THAN 43, SAID METAL BEING IN THE METALLIC STATE AND SUPPORTED ON A CARRIER SELECTED FROM THE GROUP CONSISTING OF ACTIVATED ALUMINA, ACTIVATED CHARCOAL AND KIESELGUHR, NO SOLVENT OTHER THAN A HYDROCARBON SOLVENT BEING EMPLOYED. 